Studies on the additive performance of liquid crystal blended polyacrylate in lubricating oil

Homopolymer of decyl acrylate (D) was synthesised, characterised (Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance (NMR)) and evaluated for its additive performance as antiwear (AW), pour point depressant (PPD) and viscosity modifier (VM). Physical blends of the polymer were also made with three different types of liquid crystals (each containing three samples), evaluated and the results were compared. The study indicated that additive performances (AW, VM and PPD) of the blended composites were much better in comparison to the homopolymer of polydecyl acrylates.     

High Frequency Shoots Regeneration for Mass Multiplication of Phyllanthus fraternus Webster—An Important Antiviral and Hepatoprotective Plant

An efficient, rapid, and highly reproducible regeneration protocol was successfully developed for Phyllanthus fraternus from the field-derived mature nodal segments. The explants induced multiple shoots on cytokinin containing medium. The highest frequency (99 %) and maximum number of shoots (19.75) were induced on Murashige and Skoog’s (MS) medium supplemented with 2.22 μM 6-benzylaminopurine after 3–4 weeks of culture initiation. The elongated shoots were rooted on MS medium supplemented with indol-3-butyric acid (IBA) or α-naphthalene acetic acid. Pulse treatment of microshoots promoted significant increase in the percentage of rooting and number of root regeneration per shoot. The highest rooting (100 %) and maximum number of roots (8.75) per shoot was obtained when shoots were dipped in IBA solution (0.98 mM) for 5 min and further subcultured on MS basal medium. Plantlets were successfully acclimatized and established in soil. Regenerated plants were grown normally in the field without showing any morphological variations. This cost-effective protocol will help the mass multiplication of P. fraternus for commercial propagation and high biomass production of this valuable medicinal plant.     

Vibrational studies of polar aprotic molecule in aromatic chemical and isotropic solvents: experimental and quantum chemical investigations

Raman spectroscopic technique has been used to study the intermolecular interactions and dynamics of SO, C―H and CSC stretching modes of dimethyl sulfoxide (DMSO) in binary mixtures using methyl benzene (MBN) and deuterated methyl benzene (MBNd) aromatic solvents. The Raman band of SO stretching mode has been deconvoluted into four distinct bands for neat DMSO as well as in binary mixtures. Deconvoluted bands in neat DMSO were assigned as monomer, cyclic out‐of‐phase, cyclic in‐phase and chain dimers having peak wavenumbers 1069.10, 1056.60, 1041.50 and 1027.30 cm⁻¹ respectively. Peak wavenumber of SO stretching mode shows red shift, while peak wavenumbers of C―H and CSC stretching modes show blue shift with the increase in solvent concentration. The vibrational relaxation phenomena for all the stretching modes have been studied as a function of solvent concentration. Quantum‐chemical calculations have been carried out to gain more insight into the self‐association of DMSO and in interacting environment with the solvents using ab initio and density functional theory method. The ab initio basis set is HF/6‐31 + G (d, p) for the interacting system. The hydrogen bond complexes of DMSO with MBN and MBNd using IEF‐PCM model have been calculated using B3LYP functional and 6‐31 + G(d,p) basis sets. Theoretical calculations have been compared with the experimental findings and we obtained good coherence of the results. Copyright © 2015 John Wiley & Sons, Ltd.     

Analysis of spatially extended excitable Izhikevich neuron model near instability

The dynamic response and bifurcations of high-dimensional systems endowed with hysteretic restoring forces in all degrees of freedom are investigated. Two types of hysteresis models are considered, namely the Bouc–Wen model and a differential version of the so-called exponential model of hysteresis. The numerical technique tailored for tackling high-dimensional hysteretic systems is based on an enhanced pathfollowing approach based on the Poincaré map. In particular, a five-dof mass-spring-damper-like system, with each rheological element described by the Bouc–Wen or the exponential model of hysteresis enriched by cubic and quintic nonlinear elastic terms, is investigated and a rich variety of nonlinear responses and bifurcations is found and discussed.

     

Solvent-Assisted Naked Eye Sensing of Hg2+ by a Chemoreceptor Derived from Diazocoupling of Sulfathiazole with Diethyl Malonate

Abstract

2-{[4-(Thiazol-2-ylsulfamoyl)-phenyl]-hydrazono}-malonic acid diethyl ester (R1) and 2-{[4-(5-methyl-isoxazol-3-ylsulfamoyl)-phenyl]-hydrazono}-malonic acid diethyl ester (R2) were synthesized through diazocoupling of sulfathiazole and sulfamethoxazole, respectively, with diethyl malonate. They were characterized through various spectroscopic and mass spectral studies. R2 was also characterized through a single crystal X-ray diffraction (XRD) study. Only R1 selectively recognized Hg²⁺ from a wide range of metal ions through naked-eye change. A color change from orange to olive green was observed upon addition of 1.0 equivalent of Hg²⁺ as its chloride salt to the 1 × 10^?3 M DMSO solution of R1. The role of DMSO in the sensing process appears to be the crucial one, because the solvent-assisted band of R1 at 482 nm observed in its UV-Vis spectrum in DMSO did not appear in its spectra recorded in nujol or in a polar aprotic solvent. The UV-Vis and ¹H NMR titrations revealed that the formation of six-membered 1:1 chelate between R1 and Hg²⁺ triggering the desolvation of R1

as the key step towards its sensing activity. The determination of binding stoichiometry between R1 and Hg²⁺ along with binding constant has also been discussed.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

GRAPHICAL ABSTRACT      

Hydroxo‐Bridged Dimers of Oxo‐Centered Ruthenium(III) Triangle: Synthesis and Spectroscopic and Theoretical Investigations

The homometallic hexameric ruthenium cluster of the formula [Ru^III₆(μ₃‐O)₂(μ‐OH)₂((CH₃)₃CCO₂)₁₂(py)₂] ( 1 ) (py=pyridine) is solved by single‐crystal X‐ray diffraction. Magnetic susceptibility measurements performed on 1 suggest that the antiferromagnetic interaction between the Ru^III centers is dominant, and this is supported by theoretical studies. Theoretical calculations based on density functional methods yield eight different exchange interaction values for 1 : J₁=?737.6, J₂=+63.4, J₃=?187.6, J₄=+124.4, J₅=?376.4, J₆=?601.2, J₇=?657.0, and J₈=?800.6 cm^?1. Among all the computed J values, six are found to be antiferromagnetic. Four exchange values (J₁, J₆, J₇ and J₈) are computed to be extremely strong, with J₈, mediated through one μ‐hydroxo and a carboxylate bridge, being by far the largest exchange obtained for any transition‐metal cluster. The origin of these strong interactions is the orientation of the magnetic orbitals in the Ru^III centers, and the computed J values are rationalized by using molecular orbital and natural bond order analysis. Detailed NMR studies (¹H, ¹³C, HSQC, NOESY, and TOCSY) of 1 (in CDCl₃) confirm the existence of the solid‐state structure in solution. The observation of sharp NMR peaks and spin‐lattice time relaxation (T1 relaxation) experiments support the existence of strong intramolecular antiferromagnetic exchange interactions between the metal centers. A broad absorption peak around 600–1000 nm in the visible to near‐IR region is a characteristic signature of an intracluster charge‐transfer transition. Cyclic voltammetry experiments show that there are three reversible one‐electron redox couples at ?0.865, +0.186, and +1.159 V with respect to the Ag/AgCl reference electrode, which corresponds to two metal‐based one‐electron oxidations and one reduction process.     

Kinetics and mechanism of the ruthenium(III)-catalysed oxidation of aminoalcohols by chloramine-T in perchloric acid

Summary The kinetics of the ruthenium(III) catalysed oxidation of 2-aminoethanol, 3-aminopropanol, diethanolamine and triethanolamine by chloramine-T in HClO₄ medium have been studied. The reactions exhibits first order rate dependence with respect to the oxidant and to the catalyst, and are zeroth order with respect to the substrate. The rate of oxidation is proportional to k[HClO₄]/{k+k'[HClO₄]} where k, k and k' are constants (a mixture of elementary rate constants and equilibrium constants). A suitable mechanism consistent with the observed kinetic data is proposed.     

First-order phase transformation and structural studies in Se<Subscript>85</Subscript>In<Subscript>15−x</Subscript>Zn<Subscript>x</Subscript> chalcogenide glasses

Present research work describes the crystallization kinetics and structural studies in Se₈₅In_15?xZn_x chalcogenide glasses. Bulk alloys of Se₈₅In_15?xZn_x were synthesized by melt-quenching procedure. High resolution X-ray diffraction (HRXRD) was used to confirm the amorphous nature of synthesized samples. Non-isothermal differential scanning calorimetry (DSC) measurements were performed at 5, 10, 15, 20 and 25 K min^?1 heating rates to study kinetics of crystallization in Se₈₅In_15?xZn_x. Various crystallization parameters such as glass transition (T _g), onset crystalline (T _c), peak crystallization (T _p) and melting temperature (T _m) were calculated from DSC curves. The activation energies of structural relaxation (ΔE _t) and crystallization (ΔE _c) were determined by using Kissinger, Moynihan and Ozawa approaches. ΔE _t is found to be the lowest for Se₈₅In₆Zn₉ sample which shows this sample has the highest probability of escape to a state of lower configurational energy and has greater stability. Thermal stability of various compositions was studied and found to vary with Zn content. Further, HRXRD and field emission scanning electron microscope were used for the study of first phase transformation in Se₈₅In_15?xZn_x samples.     

Benzyl isobornyl amines: a simple and practical class of NMR discriminating agents for effective chiral recognition of acids

The design and synthesis of a few simple N-benzyl derivatives of isobornyl amine is presented. The derivatives have been assessed as chiral solvating agents for effective discrimination of the signals of some acids in NMR analysis. The single crystal X-ray analysis of the salts of (R)-mandelic acid with two of the title derivatives help to understand the supramolecular interactions and assign the induced chemical shifts in ¹H NMR analysis. The title derivative is found to be suitable for quantitative determination of the enantiomeric excess of unknown enantiomeric purity as well as being efficient in resolving racemic mandelic acid.